Organosilylamines



United States Patent 3,497,539 ORGANOSILYLAMINES John C. Goossens,Scotia, N.Y., assignor to General Electric Company, a corporation of NewYork No Drawing. Filed Dec. 20, 1966, Ser. No. 603,115 Int. Cl. C07f7/18 US. Cl. 260-448.2 6 Claims ABSTRACT OF THE DISCLOSUREBis-organoaminosilalkylenes and bis-organoaminosilarylenes are used tocouple silanol stopped fluids to form gums. The process is fast and themolecular weights of the gums formed are very high with no deleteriousby-product formed during the gum formation. The gums which containrecurring silarylene units are used to make silicone rubber. The rubbersformed have the radiation resistance, hydrolytic stability and hightemperature properties which are known characteristics of polysiloxanescontaining silarylene groups.

The present invention relates to certain organosilylamines and to theemployment of these materials in combination with silanol containingorganosilicon materials to provide for the production of highermolecular weight reaction products.

The organosilylamines included by the present invention are shown by theformula,

where Y is a monovalent amino radical selected from --NZZ' and amononuclear heterocyclic amino radical having from 4 to 5 ring carbonatoms, where Z is selected from alkyl radicals and Z is selected fromhydrogen and alkyl radicals, R is selected from monovalent hydrocarbonradicals, and halogenated monovalent hydrocarbon radicals, R is adivalent radical selected from alkylene radicals, arylene radicals,alkylenearylenealkylene radicals, alkyleneoxyalkyleue radicals,alkyleneoxyarylene radicals, aryleneoxyarylene radicals, and R"TR"radicals, where R" is selected from alklene and arylene radicals, T isselected from O m m G, S, S, an Si and R' is selected from hydrogen andR radicals.

Radicals included by R of Formula 1 are for example, alkyl radicals,such as methyl, ethyl, propyl, 'butyl, hexyl, heptyl, octyl, etc. Arylradicals and halo-aryl radicals such as phenyl, xylyl, tolyl,chlorophenyl, etc., aralkyl radicals such as phenylethyl, benzyl, etc.,alkenyl radicals and cycloalkenyl radicals such as vinyl, allyl,cyclohexenyl, cycloheptenyl, etc.; alkynyl radicals such as ethynyl,l-propynyl, etc. Radicals included by R are for example, alkyleneradicals, such as methylene, ethylene, trimethylene, tetramethylene,etc., arylene radicals such as phenylene, tolylene, xylylene,naphthylene, etc.; alkyleneoxyalkylene radicals such asethyleneoxyethylene, ethyleneoxytrimethylene, etc., alkyleneoxyarylenesuch as tetramethyleneoxyphenylene, dimethyleneoxyxylylene, etc.; ar-

ice

yleneoxyarylene such as phenyleneoxyphenylene, phenyleneoxytolylene,etc. In addition R can be radicals such as (3H ii CH3 @MQ (11H; etc.Radicals included by Y are for example, pyrrolidino, piperidino, andmorpholino, as well as radicals such as ethylamino, methylethylamino,dimethylamino, diethylamino, cyclohexylamino, etc. Where R, R, R", R'can be more than one radical respectively, these radicals can be all thesame or any two or more of the aforementioned radicals.

The organosilylamines of Formula 1 can be made by efiecting contact attemperature in the range of between 30 C. to 0, between an aliphatic orheterocyclic amine and halosilylorgano compounds of the formula,

R R XSiRSiX R R where R and R are defined above, and X is a halogenradical, for example, chloro, bromo, fluoro, etc. Solvents which can beutilized to facilitate the formation of products and separation of aminesalts are for example, hexane, toluene, tetralin, etc. Recovery of theorganosilylamine can be achieved by separation of salts followed bydistillation, in accordance with standard procedures.

Methods for making some of the halosilylorgano compounds of Formula 2are well known, and are shown by Sveda Patent 2,561,429. For example, adihalosilane such as dimethyldichlorosilane can be reacted withhalogenated aromatic hydrocarbon such as p-dibromobenzene employingmetallic magnesium and anhydrous ethyl ether. In addition to theGrignard reaction other organometallic reagents can be employed such asorganolithium c0mpounds, in accordance with the method of G. Baum,Journal of Organic Chemistry, 23, 480 (1958). There also can be utilizedaddition of silanes having hydrogen attached to silicon to aliphaticallyunsaturated radicals of various organic compounds such as diallyl ether,or the platinum catalyzed addition of a silane having hydrogen attachedto silicon to a silane having aliphatically unsaturated hydrocarbonradicals attached to silicon. Some of these methods are shown inLamoreaux Patent 3,220,972 and Ashby Patents 3,159,601 and 3,159,662which are assigned to the same assignee as the present invention.

There are included by the organosilylamines of Formula 1 compounds ofthe formula,

I oHozoHHNsiomomsiNHomom),

T 6 T (CH3)zCHNHSliO SliHN CH(CH:)2

CH3 C H3 (3H3 T a NSiSiN' I I CH3 CH3 CH3 113 (o 2H5) zNs i c112oH2oHzoms iN 02115) 2 CH3 CH3 T113 T113 (CH3) zNS|i-TN H3) 2 on, CH3

etc.

Some of the halosilylorgano compounds of Formula 2 are for exampleOlSiOH2OH2CH2SiCl ClSiCH2CH2CH2O CHzCHzCHzSiCl Included by the aliphaticand heterocyclic amines which can be reacted with the halosilylorganocompounds of Formula 2 to produce the organosilylamines of Formula 1 arefor example, dimethylamine, diethylamine, isopropylamine, n-butylamine,methylethylamine, etc., piperidine, pyrrolidine, and morpholine, theheterocyclic amines are selected from the class comprising mononuclearheterocyclic amines having from 4 to 5 ring carbon atoms.

As shown in my copending application Ser. No. 452,933, filed May 3,1965, which is assigned to the same assignee as the present invention,there is described a method for making organosilicon polymers utilizingsilylamines of the formula,

(3 YSiR Y and (4) YSiR (OSiQ OSiR Y by contacting such materials withcertain silanol containing organosilicon materials, where R is aspreviously defined, Q is selected from R radicals and cyanoalkylradicals, and n is an integer equal to 1 to 1500, inclusive.

It is also the object of the present invention to provide a method formaking organosilicon polymers by contact- 4 ing silanol containingmaterial consisting essentially of chemically combined diorganosiloxyunits of the formula,

(5) Q SiO with organosilylamines of Formula 1, or silylamines of theformula,

(6) R R R R YsiR'suosiQmosiR siY R R R R and optionally in the presenceof hydroxy containing material of the formula,

( Q(Q2 )m or silylamine of the formula, (8) R SiY to provide for theproduction of organosilicon polymers consisting essentially ofchemically combined Q SiO units and R R SiRSiO R R units, where theratio of the sum of R and Q radicals to silicon has a value in the rangeof between about 1.95 to 2.4, inclusive, where R, R, Y are as definedabove, Q is selected from R radicals and cyanoalkyl radicals, n is aninteger equal to from 1 to 1500, inclusive, and m is an integer equal tofrom 3 to 1,000, inclusive.

Included by the silanol containing organosilicon materials consistingessentially of chemically combined diorganosiloxy units of Formula 5,are silanol-terminated diorganopolysiloxanes of the formula,

HO-I-iO+H I Q where n is an integer equal to 1 to 1500, inclusive.

The above silanol-terminated diorganopolysiloxane can be made bystandard hydrolysis procedures involving the hydrolysis ofdiorganodihalosilanes of the formula, Q SiX Equilibration of cyclicpolydiorganosiloxanes, or mixtures thereof, included by the formula (QSiO) Where Q can be for example, methyl or phenyl, and b is an integerequal to 3 to 8, inclusive, can provide for higher molecular weightsilanol-terminated diorganopolysiloxanes. Controlled amounts of Watercan be added to the polymer to achieve the desired final viscosity.Silanol-terminated diorganopolysiloxanes produced by the reversion ofhigher molecular weight organopolysiloxanes preferably have a viscositybetween 200 to 50,000 centipoises at 25 C. Included by thesilanol-terminated diorganopolysiloxanes of Formula 9 are polymersconsisting essentially of dimethylsiloxy units and copolymers ofdimethylsiloxy units with one or more members selected fromdiphenylsiloxy units, methylphenylsiloxy units, methylcyanoethylsiloxyunits, methyltrifiuoropropylsiloxy units, etc. These polymers can havemajor amounts of either diphenylsiloxy units, or dimethylsiloxy units.

The silanol containing organopolysiloxanes of Formula 7 can be made byequilibrating a mixture of from 0.01 to 20 mole percent of Q SiO units,and mole percent to 99.9 mole percent of Q SiO units. The silanolcontaining organopolysiloxanes of Formula 9 can contain from 0.02 to 18percent by weight of hydroxy radicals attached to silicon, based on thetotal weight of silanol-containing organopolysiloxane.

There are provided by the method of the present invention organosiliconfluids having viscosities from about 30 centipoises to as high as100,000 centipoises, or higher at 25 C., which can besilanol-terminated, or terminated with Q SiO units or R SiO units andconsist essentially of chemically combined R SiO units and R R SiRSiO RR units. The employment of silylamine of Formula 8, or silanolcontaining organopolysiloxanes of Formula 7, in

combination with the organosilylamine of Formula 1 and silanolcontaining organopolysiloxane of Formula 9, in an amount sufficient toprovide for a ratio of the sum of Q and R radicals per silicon atom,having a value greater than 2, and up to about 2.4, inclusive, canprovide for fluids having either terminal Q SiO units, R SiO units or amixture of such units. In instances where silanol-terminated fluids aredesired, mixtures of organosilylamines of Formula 1 andsilanol-terminated organopolysiloxanes of Formula 9 can be employedwhich are free of silylamine of Formula 8, or silanol containingorganopolysiloxane of Formula 7, where the ratio of Y radicals oforganosilylamine to silanol radicals of silanol-terminatedorganopolysiloxane has a value less than one. Room temperaturevulcanizing organosilicon compositions filled 'with for example, silicafiller, can be made from the afore-described silanol-terminatedorganosilicon fluids by employing ethylpolysilicate in combination witha metal soap catalyst as utilized in Berridge Patent 2,843,555 assignedto the same assignee as the present invention. Also,organoacyloxysilanes such as methyltriacetoxy silane can be employedwhich are shown in Smith et al. Patent 3,293,204, also assigned to thesame assignee as the present invention.

There are also provided by the present invention, organosilicon gumswhich can be either silanol-terminated, or terminated with Q SiO units,R SiO units, or mixtures thereof. These gums can have viscositiesbetween about 500,000 centipoises to as high as 650 million centipoisesat C. The employment of sufficient organosilylamine of Formula 1 incombination with silanol-terminated organopolysiloxane of Formula 9 toprovide for a ratio of Y radicals to silanol radicals having a value ofat least one, will provide for effective results. A proportion ofsufficient silylamine of Formula 8 or silanol containingorganopolysiloxane of Formula 7 should be employed in combination withorganosilylamine of Formula 1, and silanol-terminated organopolysiloxaneof Formula 9 to provide for a ratio of the sum of Q and R radicals persilicon having a value of from greater than 2 to about 2.001 inclusive,where polymers are desired having terminal R SiO units, Q SiO units, ormixtures thereof.

The organosilicon polymers or gums which can be made in accordance withthe practice of the invention consist essentially of chemically combinedQ SiO and R R SiR'SiO B. R units, and contain less than 1 percent byweight of volatiles based on the weight of the gum. Some of the gums canbe employed in applications similar to the polymer shown by Agens Patent2,448,756, Sprung et' al. Patent 2,448,556, Marsden Patent 2,521,528,etc., all assigned to the same assignee as the present invention. Thesegums can be milled with to 300 parts of filler, per 100 parts of gum.Such fillers include reinforcing fillers such as fumed silica, as wellas extending fillers, such as titanium oxide, etc. In addition,conventional peroxide catalyst also can be incorporated. With respect tothe organopolysiloxane gums made in accordance with the practice of thepresent invention, those consisting essentially of chemically combineddimethylsiloxy units can have molecular weights up to 2 million. Thegums made in accordance with the invention contain less than 1 percentby weight of volatiles based on the weight of the gum.

For example, some of the gums which can be made in accordance with thepractice of the invention can have the average formula such as where Acan be OH or C 11 t is an integer having an average value of from 3 to6, inclusive, and u is an integer having an average value of from to1,000, inclusive,

om CZHACN s1 0 s10 SiO siwmnotrr CH CH3 I J on, em 031131 3 '1SiCflHiSiO s10 Si (c1193 CH3 CH3 CH; 50 I1 Where v is an integer havinga value of from 2 to 30, w is an integer having a value of from 2 to 3,and x is an integer having a value of from 5 to 50.

The process of the present invention can be practiced by mixing theorganosilylamine and the silanol containing organosilicon material at atemperature between 30 C. to 200 C. Preferably temperatures between -l0C. to C. can be employed. The order of addition of the various reactantsis not critical. However, in instances where monofunctional silylamineof Formula 8 is employed in combination with the organosilylamine ofFormula 1, it is preferred to add the monofunctional silylamine prior tothe organosilylamine. An amount of 0.001 to 2 parts of monofunctionalsilylamine of Formula 8, to organosilylamine of Formula 1 can beemployed.

It is preferred to practice the method of the invention undersubstantially anhydrous conditions to preclude any undue hydrolysis of Yradicals of the organosilylamine before intercondensation is achieved,with silanol containing organosilicon material. In instances wheresubstantially anhydrous conditions are employed, rapid addition ofexcess silylamine can impede further intercondensation. However, theintroduction of moisture will provide for further intercondensation bycreating further silanol due to the hydrolysis of terminal Y radicals.Experience has shown that complete intercondensation is substantiallyretarded if an organic solvent is utilized. In order to facilitatestirring however, minor amounts of an inert organic solvent such as lessthan 10 percent by weight of the reaction mixture can be introduced toreduce the viscosity of intercondensation product. For example, benzene,xylene, toluene, and the like can be used.

Excess of the organosilylamine, beyond that quantity required to effectintercondensation of silanol with silylamine radicals, such as inamounts suflicient to provide for from 1 to 5 Y radicals, per silanolradical, can provide for effective results.

Reactions are generally most conveniently performed at atmosphericpressure conditions. However, pressures of below atmospheric can beutilized. Recovery of the desired product resulting from the contact ofthe organosilylamine with the silanol containing material can be readilyachieved by allowing the mixture to achieve a maximum viscosity and thenremoving any unreacted material or by-product at a reduced pressure.

In order that those skilled in the art will be better able to practicethe invention, the following examples are given by way of illustration,and not by way of limitation. All parts are by weight.

Example 1 There were added with stirring 280 parts of isopropylamine toa solution of 263 parts of l,4-bis(dimethyl chlorosilyl)benzenedissolved in 1700 parts of dry toluene. The isopropylamine was addeddropwise and the mixture was cooled externally with ice during theaddition. When the addition was complete, the mixture was heated to 75 7to 80 C. for 2 hours. The amine salt was filtered off and the filtratewas distilled to yield 107.5 parts of a product having a boiling pointof 110 C. at 0.2 mm. Based on its infrared spectrum, the product was1,4-bis(isopropylaminodimethylsilyl)benzene of the formula,

CH3 (CI-I )zCHNIISi slNHCH(CH3)2 CH3 CH Example 2 There was added at /2hour intervals, 0.09 part of the organosilylamine of Example 1, to 20parts of a silanolterminated dimethylpolysiloxane which was stirred andheated at 60 C. After about 1.2 part of the organosilylamine had beenadded a gum had formed having an intrinsic viscosity 1] in toluene at 25C. of 1.8 dl/g. A portion of this gum was compounded with 40 parts offumed silica and 2% by weight of the gum of benzoyl peroxide. A 20 milsheet was press-cured at 150 C. for 10 minutes. There was obtained anelastomer having a tensile of 600 (p.s.i.) and an elongation of 250(percent).

Example 3 There were added 49 parts of dimethylchlorosilane to a mixtureof 58 parts of dimethylvinylchlorosilane and 30 parts, per million ofthe resulting mixture, of a platinum catalyst shown by Lamoreaux Patent3,220,972 while the mixture was stirred. The addition was performed at atemperature of 65 C. After the addition was complete, the mixture washeated to 120 C. for 1 hour. There was obtained a 90% yield of1,2-bis,dimethylchlorosilyl)ethane which solidified at 32 C.

There were added dropwise, 150 parts of diethylamine to a stirredsolution at 10 C. of 100 parts of the abovebis(dimethylchlorosilyl)ethane dissolved in 1000 parts of dry toluene.When the addition was complete, the mixture was heated to 110 C. for /2hour. The amine salt was filtered off and the filtrate was distilled toyield 81 parts of product boiling at 80 C. at 0.2 mm. Based on itsinfrared spectrum, the product Was l,2-bis(dimethyldiethylaminosilyl)ethane of the formula,

CH3 CH Example 4 There was added at /2 hour intervals, 0.09 part of theabove bis(dimethyldiethylaminosilyl)ethane, to 40 parts of asilanol-terminated polydimethylsiloxane at 100 C. which had a viscosityof 3200 centipoises at 25 C. After 0.72 part of the organosilylarninehad been added, there was obtained a gum having an intrinsic viscosity[1 in tolune at 25 C. of 1.4 dl/g. It was compounded with 40 parts ofsilica filler and presscured at 150 C. for 10 minutes with 2% by weightof benzoyl peroxide. An elastomer was obtained having a tensile (p.s.i.)of 790, and an elongation (percent) of 165 at break.

Example There were added dropwise 205 parts of dimethylchlorosilane overa period of several hours to 98 parts of diallylether containing 30parts of the platinum catalyst of Example 3, per million parts ofdiallylether. The resulting mixture was then heated under reflux for 24hours. Distillation of the mixture yielded 85 parts of a product havinga boiling point of 107 to 110 C. at 0.5 mm. The product wasbis(dimethylchlorosilylpropyl)ether whose identity was confirmed bychlorine analysis and its infrared spectrum.

There was added 85 parts of the abovebis(dimethylchlorosilylpropyl)ether to 80 parts of isopropylamine in 650parts of dry toluene cooled in an ice bath. During the addition, themixture was vigorously stirred. When the for 1.5 hours. The amine saltwas filtered off and the addition was complete, the mixture was heatedto 110 C.

8 filtrate was distilled to yield 30 parts of a product having a boilingpoint of 124-126 C., at 0.3 mm. Based on its method of preparation andits infrared spectrum, the product wasbisdimethylisopropylaminosilylpropyl)ether of the formula,

Example 6 Increments of the bis(silylamino)ether of Example 5 were addedto 40 parts of the silanol-terminated polydimethylsiloxane of Example 4at C. After 1.5 part of the amine had been added, there was obtainedafter several days, a soft gum having an intrinsic viscosity [1;] intoluene at 25 C. of 0.95 dl/g.

Example 7 In accordance with the procedure of Example 3, 55 parts ofdimethylc'hlorosilane were added to 65 parts of dimethylallylchlorsilaneat a temperature of C. in the presence of 30 parts of platinum catalyst,per million parts of mixture. There was obtained1,3-bis(dimethylchlorosilyl)propane; B.P. 93 C., at 9 mm. Thecorresponding bis-(dimethylaminodimethylsilyl)propane was prepared bythe following procedure.

There were added 55 parts of dimethylamine to 65 parts of Cl(CH SiCH CHCH Si(CH Cl in 550 parts of dry toluene at 0 C. When the addition wascompleted, the mixture was heated to C. for 30 minutes. The mixture wasallowed to cool. It was then filtered and the filtrate was distilled.There was obtained 33 parts of a product having the formula,

(CH N(CH SiCH CH CH Si (CH N (CH 2 based on its method of preparationand its vapor phase chromatograph.

A gum having an intrinsic viscosity [1;] in toluene at 25 C. of 1.1 dl/g-was prepared by mixing the above bis(dimethylaminosilyl)propane withthe silanol-terminated polymer of Example 6. The gum was compounded with40 parts of filler, and press-cured with 1.6% benzoyl peroxide inaccordance with the previously described procedure. A rubber Wasobtained having 1,230 tensile (p.s.i.), and 365 (percent) elongation atbreak.

Example 8 By the method of G. Baum [1. Org Chem. 23, 480 (1958]4,4'-bis(dimethylchlorosilylphenyl)ether is prepared by reaction of a1.5 N n-butyl lithium solution with 4,4-bis(bromophenyl)ether in benzenesolution, followed by 3 hours reflux with dimethyldichlorosilane. Theproduct is distilled from the reaction mixture and then reacted with a10% stoichiometric excess of dimethylamine in hexane. The mixture isfiltered, stripped and distilled. Based on method of preparation thereis obtained CH3 (CH3)2NS1 O SiN(CH3)2 A mixture of 110 parts of theabove organosilylamine, and parts of a silanol-terminatedpolydimethylsiloxane having 10.5% by weight OH is stirred at l0 C. undernitrogen. It is gradually heated to 60 C. with stirring until no furtherevolution of dimethylamine is effected. There is obtained asilanol-terminated fluid having a molecular weight of about 2500 andconsisting of chemically combined S10 units and S1 0 SiO CH3 CH3 units.

A mixture of 100 parts of the above fluid and 10 parts ofmethyltriacetoxysilane is blended under atmospheric conditions. Anelastomer is obtained after hours showing valuable insulatingproperties.

While the foregoing examples have been limited to only a few of the verymany organosilylamines of the present invention, it should be understoodthat the present invention is directed to a much broader class oforganosilylamines as shown by Formula 1, which can be made by effectingcontact between halosilylorgano compounds of Formula 2 and variousaliphatic or heterocyclic amines previously described.

It also should be understood that the present invention is also directedto a method for making a much broader class of organopolysiloxanepolymers consisting essentially of chemically combined units, and

R R SiRSiO R R R R YSiRSiY R R where Y is a monovalent organoaminoradical selected from NZZ' and a mononuclear heterocyclic amino radicalhaving from 4 to 5 ring carbon atoms, where Z is selected from alkylradicals, and Z is selected from hydrogen and alkyl radicals, R isselected from the class consisting of monovalent hydrocarbon radicals,and 40 halogenated monovalent hydrocarbon radicals, R is a divalentradical selected from alkylene radicals, arylene radicals,alkylenearylenealkylene radicals, alkyleneoxyalkylene radicals,alkyleneoxyarylene radicals, aryleneoxyarylene radicals, and R"TR"radicals, where R" is selected from alkylene and arylene radicals and Tis selected from where R' is selected from R radicals.

2. An organosilylamine of claim 1, having the formula,

3. An organosilylamine of claim 1 having the formula,

CH3 CH3 (C2115) Z 2H4 (021192 CH3 CH3 4. An organosilylamine of claim 1having the formula,

CH3 CH3 (CH3)2HCHNSiC3HaOC3H SiNHCH(CH3)2 CH; CH: 5. An organosilylamineof claim 1 having the formula,

CH3 CH3 (CH3)2NSiC3 a 3)2 CH3 CH3 6. An organosilylamine of claim 1having the formula,

CH3 (CH3) 2NSi O SiN (CH C H: CH

References Cited UNITED STATES PATENTS 2,739,638 3/1956 Lewis et al.260-4482 XR 2,883,395 4/1959 Rogers et al. 260-448.2 XR 3,072,594 1/1963Shultz et al. 260-4482 XR 3,133,110 5/1964 Morehouse et al. 260-44823,305,525 2/1967 Goossens 260-4482 XR 3,336,352 8/1967 Omietanski260-4482 3,189,576 6/1965 Sweet 260-46.5

OSCAR R. VERTIZ, Primary Examiner P. F. SHAVER, Assistant Examiner US.Cl. X.R.

